含侧链苯炔基的热固性聚酰亚胺薄膜

采用3,3,′4,4′-联苯四酸二酐(3,3,′4,4-′BPDA)和3种二胺,3,5-二氨基-4′-苯炔基二苯甲酮(DPEB)、4,4′-二氨基二苯醚(4,4-′ODA)及4,4′-二氨基二苯甲酮(4,4-′DABP),以苯酐(PA)为封端剂制备了不同比例的带苯炔侧基的聚酰亚胺薄膜,采用DMTA、TGA和力学性能测试等分析技术对侧链含苯乙炔基的聚酰亚胺膜的性能进行了表征。

Preparation and characterization of polyimide/Al2O3 hybrid films by sol-gel process

A sol-gel process has been developed to prepare polyimide (PI)/Al2O3 hybrid films with different contents of Al2O3 based on pyromellitic dianhydride (PMDA) and 4,4'-oxydianiline (ODA) as monomers. FESEM and TEM images indicated that Al2O3 particles are relatively well dispersed in the polyimide matrix after ultrasonic treatment of the sol from aluminum isopropoxide and thermal imidization of the gel film. The dimensional stability, thermal stability, mechanical properties of hybrid PI films were improved obviously by an addition of adequate Al2O3 content, whereas, dielectric property and the elongation at break decreased with the increase of Al2O3 content. Surprisingly, the corona-resistance property of hybrid film was improved greatly with increasing Al2O3 content within certain range as compared with pure PI film.

Novel Sulfonated Polyimide Ionomers by Incorporating Pyridine Functional Group in the Polymer Backbone

A series of sulfonated polyimides (SPIs) containing pyridine ring in the polymer backbone were synthesized by the polycondensation of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTDA), 5-(2,6-bis(4-arninophenyl)pyridin-4-yl)-2-methoxy benzene sulfonic acid (SDAM), and 4,4'-diaminodiphenyl ether (ODA). Flexible, transparent, and tough membranes were obtained. Property study revealed that all the membranes displayed high thermal stability with the desulfonation and decomposition temperature higher than 290 and 540 degrees C, respectively, as well as good mechanical property with Young's modulus larger than 1.0 GPa, maximum strength (MS) on a scale of 60-80 MPa, and elongation at break (EB) ranged from 41.79 to 75.17%.

Nucleation and growth of glycine crystals with controllable sizes and polymorphs on Langmuir-Blodgett films

Control of crystal polymorph and size is very important in many application fields. Herein we demonstrate that Langmuir-Blodgett (LB) films of stearic acid (SA) and octadecylamine (ODA) can serve as templates and generate different polymorphs of glycine crystals. In the neutral aqueous solutions, gamma-glycine crystallizes on LB films of ODA while the polymorphic outcome becomes the (x-form on LB films of SA. These observed results could be explained by the electrostatic interactions and geometric lattice matching at the LB film/crystal interfaces, respectively. By keeping the appropriate supersaturation, we have successfully controlled the number of crystals grown on LB films; for example, in some certain cases, only one piece of crystal was grown on LB films in solution. Therefore, large crystals of centimeter size could be prepared. These experimental results suggest a new approach to produce an organic crystal with bulk scale.

Shear-enhanced crystallization of a thermoplastic polyimide derived from 3,3 ',4,4 '-oxydiphthalic dianhydride and 4,4 '-oxydianiline

The aim of this work is to investigate the effect of consecutive shear on the crystallization of an amorphous aromatic polyimide (PI) derived from 3,3',4,4'oxydiphthalic dianhydride (3,3',4,4'-ODPA) and 4,4-oxydianiline (ODA). At 260 degrees C, the increase of shear rate or shear time leads to the increase of crystallinity. Indeed, increasing shear rate can also accelerate the crystallization behavior. Moreover, it was found that a new melting peak appeared at higher temperature for long time or high rate sheared sample. The enhancement of crystallization behavior appears directly linked to the increase of crystal thickness. Particularly, the effect of shear temperature was investigated, and the results revealed that the crystallization of the PI was more sensitive to shear at 260 degrees C, which was 10 degrees above the glass transition temperature (250 degrees C) of the PI. Possible mechanism was proposed to illustrate the effect of consecutive shear on the crystallization of the PI polymer.

Synthesis and characterization of novel sulfonated polyimides from 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid

A novel sulfonated diamine monomer, 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid (BAPNDS), was synthesized. A series of sulfonated polyimide copolymers were prepared from BAPNDS, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and nonsulfonated diamine 4,4'-diaminodiphenyl ether (ODA). Flexible, transparent, and mechanically strong membranes were obtained. The membranes displayed slightly anisotropic membrane swelling. The dimensional change in thickness direction was larger than that in planar. The novel SPI membranes showed higher conductivity, which was comparable or even higher than Nafion 117. Membranes exhibited methanol permeability from 0.24 x 10(-6) to 0.80 X 10(-6) cm(2)/s at room temperature, which was much lower than that of Nafion (2 x 10-6 CM2/s). The copolymers were thermally stable up to 340 degrees C. These preliminary results have proved its potential availability as proton-exchange membrane for PEMFCs or DMFCs.

Water resistant sulfonated polyimides based on 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BNTDA) for proton exchange membranes

A series of sulfonated polyimides (SPIs) were synthesized in in-cresol from 4,4'-binaphthyl- 1,11,8,8'-tetracarboxylic dianhydride (BNTDA), 4.4'-diaminodiphenylether-2,2-disulfonicacid (ODADS), and 4.4'-diamino-diphenyl ether (ODA) in the presence of triethylamine and benzoic acid. The resulted polyimides showed much better water resistance than the corresponding sulfonated polyimides from 1,4,5,8-naphthatenetetracarboxylic dianhydride (NTDA) and ODADS, which is contributed to the higher electron density in the carbonyl carbon atoms of BNTDA. Copolyimides S-75 and S-50 maintained their mechanical properties and proton conductivities after aging in water at 100 degrees C for 800 h. The proton conductivity of these SPIs was 0.0250-0.3565 S/cm at 20 degrees C and 100% relative humidity (RH), and increased to 0.11490.9470 S/cm at 80 degrees C and 100% RH. The methanol permeability values of these SPIs were in the range of 0.99-2.36 x 10(-7) cm(2)/S, which are much lower than that of Nafion 117 (2 x 10(-6) cm(2)/s).

Morphology of polyimide fibers derived from 3,3 ',4,4 '-biphenyltetracarboxylic dianhydride and 4,4 '-oxydianiline

As one member of high performance fibers, aromatic polyimide fibers possess many advantages, such as high strength, high modulus, high and low temperature resistance, and radiation resistance. However, the preparation of the high performance fibers is so difficult that the commercial fibers have not been produced except P84 with good flame retardancy. In this report, a polyimide was synthesized from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-oxydianiline (ODA) and the fibers were prepared from its solution by a dry-jet wet-spinning process. The formation of the as-spun fibers in different coagulation bath composition was discussed. Scanning electron microscope (SEMI) was employed to study the morphology of the as-spun fibers. As a result, the remnant solvent existed in the as-spun fibers generated from coagulation bath of alcohol and water. There were many fibrils and microvoids with the dimension of tens of nanometers in the fibers. One could observe the obvious fibrillation and the drawn fibers.

Synthesis and properties of novel polyimides derived from 2,2 ',3,3 '-benzophenonetetracarboxylic dianhydride

A new synthetic route to 2,2',3,3'-BTDA (where BTDA is benzophenonetetracarboxylic dianhydride), an isomer of 2,3',3',4'-BTDA and 3,3',4,4'-BTDA, is described. Single-crystal X-ray diffraction analysis of 2,2',3,3'-BTDA has shown that this dianhydride has a bent and noncoplanar structure. The polymerizations of 2,2',3,3'-BTDA with 4,4'-oxydianiline (ODA) and 4,4'-bis(4-aminophenoxy)benzene (TPEQ) have been investigated with a conventional two-step process. A trend of cyclic oligomers forming in the reaction of 2,2',3,3'-BTDA and ODA has been found and characterized with IR, NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and elemental analyses. Films based on 2,2',3,3'-BTDA/TPEQ can only be obtained from corresponding polyimide (PI) solutions prepared by chemical imidization because those from their polyamic acids by thermal imidization are brittle. PIS from 2,2',3,3'-BTDA have lower inherent viscosities and worse thermal and mechanical properties than the corresponding 2,3',3',4'-BTDA- and 3,3',4,4'-BTDA-based PIs. PIs from 2,2',3,3'-BTDA and 2,3',3',4'-BTDA are amorphous, whereas those from 3,3',4,4'-BTDA have some crystallinity, according to wide-angle X-ray diffraction.

Synthesis and properties of polyimides derived from cis- and trans-1,2,3,4-cyclohexanetetracarboxylic dianhydrides

Cis-1,2,3,4-cyclohexanetetracarboxylic dianhydride (cis-1,2,3,4-CHDA) was synthesized. It was found that under such conditions as heating or boiling in acetic anhydride, cis-1,2,3,4-CHDA could be converted to its trans-isomer. The process of thermal isomerization was monitored by H-1 NMR spectra and the mechanism of conversion was proposed. Their absolute structures of cis- and trans-1,2,3,4-CHDAs were elucidated by single crystal X-ray diffraction. The polycondensations of cis- and trans-1,2,3,4-CHDAs with aromatic diamines such as 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), 4,4'-diamino-3,3'-dimethyldiphenylmethane (DMMDA), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2-bis[4-(4-aminophenoxy)phenyl] propane (BAPP) were studied. It is easy to obtain higher molecular weight polyimides from trans-1,2,3,4-CHDA using conventional one-step or two-step methods. However, higher molecular weight polyimides derived from cis-1,2,3,4-CHDA could not be prepared by the usual methods (solid content ca. 10%) owing to the trend of forming cyclic oligomers.

Fabrication, characterization and conductivity of organic-inorganic hybrid Langmuir-Blodgett films based on polyquinoline and rare earth-substituted heteropolymolybdate

The organic/inorganic hybrid Langmuir-Blodgett (LB) films were obtained by the compact organization of poly(1,2-dihydro-2,2,4-trimethyl)quinoline (PQ), octadecylamine (ODA) and rare earth-substituted heteropolymolybdates. They were characterized by surface pressure-area (pi-A) isotherms, absorption spectra, fluorescence spectra, atomic force microscope (AFM) and scanning tunneling microscopy (STM). The atomic force microscope revealed a granular surface texture of nanosized rare earth-substituted heteropolymolybdate. The scanning tunneling microscopy indicated that the hybrid LB films containing rare earth-substituted heteropolymolybdates had the better electrical conductivity than LB film of PQ/ODA.

Polyimides from isomeric oxydiphthalic anhydrides

2,2',3,3'-Oxydiphthalic dianhydride (2,2',3,3'-ODPA) and 2,3,3',4'-ODPA were synthesized from 3-chlorophthalic anhydride with 2,3-xylenol and 3,4-xylenol, respectively. Their structures were determined via single-crystal X-ray diffraction. A series of polyimides derived from isomeric ODPAs with several diamines were prepared in dimethylacetamide (DMAc) with the conventional two-step method. Matrix-assisted laser desorption/ionization time-of-flight spectra showed that the polymerization of 2,2',3,3'-ODPA with 4,4'-oxydianiline (ODA) has a greater trend to form cyclic oligomers than that of 2,3,3',4'-ODPA. Both 2,2',3,3'-ODPA and 2,3,3',4'-ODPA based polyimides have good solubility in polar aprotic solvents such as DMAc, dimethylformamide, and N-methylpyrrolidone. The 5% weight-loss temperatures of all polyimides were obtained near 500 degreesC in air. Their glass-transition temperatures measured by dynamic mechanical thermal analysis or differential scanning calorimetry decreased according to the order of polyimides on the basis of 2,2',3,3'-ODPA, 2,3,3',4'-ODPA, and 3,3',4,4'-ODPA. The wide-angle X-ray diffraction of all polyimide films from isomeric ODPAs and ODA showed some certain extent of crystallization after stretching. Rheological properties revealed that polyimide (2,3,3',4'-ODPA/ODA) has a comparatively lower melt viscosity than its isomers, which indicated its better melt processability.

Polyimides derived from mellophanic dianhydride

The synthesis of mellophanic dianhydride (MPDA), an isomer of pyromellitic dianhydride (PMDA), was studied. A trend of forming cyclic oligomers in the reactions of MPDA with 4,4'-oxydianiline (ODA) or 4,4'-methylenedianiline (MDA) in DMAC was found. The cyclic dimer from MPDA/MDA was isolated and fully characterized, including an X-ray crystallographic analysis. The reactions of MPDA with aromatic diamines were found much more complicated than those of PMDA. A model study was performed to clarify the reactions. Several byproducts were isolated and characterized, so that, in an usual two-step process to prepare polyimides, imide, amide linkage, and carboxylic group may be involved in the polymer structure. The water, either existing in solvent or being generated during the imidization, is the main reason for the side reactions. The properties of some polyimides derived from MPDA and diamines were tested and compared with those of the isomeric polyimides derived from PMDA.

Improvement of mechanical property of polyimide blends with Co-60-irradiation

Radiation effects on polyimide blends' were studied at different irradiation temperatures and with different irradiation doses. The irradiation polyimides were the blends of linear polyimide (HQDPA/ODA) and 4-phenylethynyl phthalic anhydride end-capped oligomer polyimide. The tensile strength and the elongation at break of irradiated films were determined as the function of irradiation temperature and dose. Under proper conditions crosslinking reaction occurred when the polyimide blends were irradiated at high temperature. The mechanical properties of irradiated polyimide blends were found to be different from the linear polyimide.